Composition

ABSTRACT

There is provided composition comprising i) a thermoplastic polymer ii) a compound having the formula 
                 
 
wherein R 1 , R 2  and R 3  are independently selected from an acyl group or a hydrogen atom, wherein at least one of R 1 , R 2  and R 3  is an acyl group (a short acyl group) having from 2 to 6 carbon atoms, wherein at least one of R 1 , R 2  and R 3  is a branched chain acyl group (a long acyl group) consisting of a saturated chain having 10 to 20 carbon atoms and a hydrophilic branch group.

RELATED APLLICATION

This application is a division of application Ser. No. 09/642,480, filedAug. 18, 2000, now U.S. Pat. No. 6,734,241, which is acontinuation-in-part of Danisco A/S or Nielsen, PCT/IB00/01773, filedAug. 9, 2000 with the International Bureau of WIPO designating theUnited States. This application also claims priority from U.S.application Ser. No. 60/167,923 filed Nov. 29, 1999, and United KingdomApplication 9919683.4, filed Aug. 19, 1999. Each of these applicationsand patents and each document cited or referenced in each of theseapplications and patents, including during any prosecution (“applicationcited documents”), and each document cited or referenced in each of theapplication cited documents, are hereby incorporated herein byreference. In addition, each document cited in this text (“herein citeddocuments”) and each document cited or referenced in each of the hereincited documents, and each product data sheet for each commerciallyavailable product mentioned herein, are hereby incorporated herein byreference.

The present invention relates to a composition. In particular, thepresent invention relates to a composition comprising a thermoplasticpolymer and a compound which acts as a plasticiser.

The manufacturing properties of thermoplastic polymers, for example theextruding properties of such polymers, is often modified/enhanced by theaddition of plasticisers thereto. As acknowledged in the prior art, suchas in U.S. Pat. No. 4,426,477, there is a tendency toward avoiding thecommonly used plasticisers such as dioctyl adipate (DOA) and phthalateplasticisers such as dioctyl phthalate (DOP). The safety of theseplasticisers has been called into question, particularly in certainapplications.

U.S. Pat. No. 4,426,477 discloses plasticisers based on glycerol esters.The plasticisers consist of compounds prepared by the acylation ofglycerol. The compounds comprises triesters, wherein approximately twoof the acyls have two carbons and the remaining one acyl has from 10 to14 carbons. The compounds of U.S. Pat. No. 4,426,477 provide aplasticising effect. However, in certain applications the plasticisershave a volatility such that they may migrate out of the thermoplasticpolymer in which they are incorporated, such as PVC.

In a first aspect the present invention provides a compositioncomprising i) a thermoplastic polymer ii) a compound having the formula

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbon atoms, wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)consisting of or having a saturated chain having 10 to 20 carbon atomsand a hydrophilic branch group.

Preferably two of R₁, R₂ and R₃ are short acyl groups as described aboveand the other of R₁, R₂ and R₃ is a long acyl group as described above.In this aspect, the compound may be of the formula

Preferably the hydrophilic branch group is a group selected from acyland derivatives thereof. Preferred derivatives include groups of theformula —O-acyl.

Preferably the hydrophilic branch group is a group of the formula

wherein p is from 0 to 4 or 0 to 3.

In a preferred aspect of the present invention the chain of the longacyl group consists of or has a saturated chain having 14 to 20 carbonatoms. In a more preferred aspect, the chain of the long acyl groupconsists of or has a saturated chain having 16 to 20 carbon atoms.

Preferably the long acyl group is of the formula

wherein n is from 10 to 20 and m is 2n, and wherein p is from 0 to 4 or0 to 3.

Preferably n is from 16 to 20, more preferably from 16 to 18, yet morepreferably 17.

Preferably the group CnHm is a straight chain hydrocarbon group.

In a highly preferred aspect the long acyl group is a group of theformula

wherein x is from 7 to 10, preferably x is 10, and y is 2x, and whereinp is from 0 to 4 or 0 to 3, preferably p is 0.

Preferably the group CxHy is or comprises a straight chain hydrocarbongroup.

In a highly preferred aspect the long acyl group is a group of theformula

In a preferred aspect of the present invention the short acyl group isor comprises an acyl group having from 2 to 5 carbon atoms. In a morepreferred aspect, the short acyl group is or comprises an acyl grouphaving 2 carbon atoms. The short acyl group is preferably of the formula

Preferably the short acyl group and the hydrophilic branch group containthe same number of carbon atoms. In a highly preferred aspect thehydrophilic branch group is a group of the formula

and the short acyl group is of the formula

wherein p=q and is from 0 to 4 or 0 to 3.

In certain aspects, it is desirable for the short acyl groups to bepresent in a maximum amount with respect to the total amount glyceroland esters thereof present in the composition. Preferably the short acylgroup is present in an amount, on average, of no greater than 2 molesper mole of glycerol and esters thereof present in the composition.

In certain aspects, it is desirable for the long acyl groups to bepresent in a minimum amount with respect to the total amount glyceroland esters thereof present in the composition. Preferably the long acylgroup is present in an amount, on average, of at least 0.4 moles,preferably from 0.9 to 2 moles, more preferably from 0.9 to 1 moles permole of glycerol and esters thereof present in the composition.

It may also be preferred for the majority of the glycerol present in thecomposition to be fully acylated. Accordingly, in a preferred aspect thetotal amount of acyl groups is, on average, 2.7 to 3.0 moles per mole ofglycerol and esters thereof.

The compound of the present invention may be prepared byinteresterification between glycerol and one or more oils, includingnatural oils and hardened natural oils followed by acylation. Thus, thecompound of the present invention may be the product of a two partprocess comprising (i) an interesterification between glycerol and anoil selected from castor oil, including hardened castor oil, unhardenedcastor oil and mixtures thereof, and (ii) acylation.

Thus in a further aspect the present invention provides a process forthe preparation of a compound having the formula

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom; wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbon atoms or from 2 to 5carbons; wherein at least one of R₁, R₂ and R₃ is a branched chain acylgroup (a long acyl group) consisting of or having a chain having 10 to20 carbon atoms and a hydrophilic branch group;the process comprising the steps of:

-   (i) interesterification between glycerol and triglyceride compound    having the formula    wherein each of R₁, R₂ and R₃ is a fatty acid group consisting of or    having a chain having 10 to 20 carbon atoms, to provide a    composition comprising glycerol, monoglyceride, diglyceride and/or    triglyceride;-   (ii) optionally isolating the monoglyceride and/or diglyceride from    the composition;-   (iii) acylating the monoglyceride and/or diglyceride or the    composition containing the same.

In the process of the present invention the chain having 10 to 20 carbonmay be saturated or unsaturated.

The process of the present invention may utilise, for example, castoroil or hardened castor oil. The compound of the present invention may beprepared from hardened castor oil. A typical fatty acid profile ofcastor oil and hardened castor oil is given below.

Castor Oil Hardened Castor Oil Fatty Acid Content [%] Fatty Acid Content[%] Palmitic (C16) 1.0 Palmitic (C16) 1.3 Stearic (C18) 1.1 Stearic(C18) 9.3 Oleic (C18:1) 3.8 Oleic (C18:1) 0.9 Linoleic (C18:2) 4.4Linoleic (C18:2) 0.2 Linolenic (C18:3) 0.5 Arachidic (C20) 0.7 Gadoleic(C20:1) 0.5 Ricinoleic hard 84.9 Ricinoleic (C18:1-OH) 87.4 (C18-OH)

The nomenclature in parenthesis is Cxx:y where xx is the fatty acidcarbon number and y indicates number of double bonds. Ricinoleic acid,hard (also known as 12-hydroxy stearic acid) has a hydroxyl group (OH)on the 12^(th) carbon.

In this aspect the product based on the castor oil, or indeed a productbased on another oil, may be synthesised as follows. These syntheticroutes are given by way of example only. Other routes would beappreciated by a person skilled in the art.

Route 1

Castor oil and glycerol are reacted to produce an equilibrium mixture ofdifferent glycerol esters. This mixture can be distilled andsubsequently acetylated to provide the desired end products. This routeis illustrated below.

The second step comprising the removal of the glycerol followed bydistillation is optional. In other word the mixture of glycerol,glycerol monoester, glycerol diester, and glycerol triester may directlyacetylated with acetic anhydride to form a mixture of acetylatedproducts. The acetylated monoglyceride or the mixture of acetylatedproducts may have a yellowish colour. The yellowish product may bedistilled. The distilled product is clear.

Depending on the ratio between castor oil and glycerol and depending onthe reaction conditions, the described process provides differentglycerol ester mixtures. The glycerol monoester is typically 45-65% andmay be up to 65%. This is achieved in a typical reaction mixture. Such acomposition may then, optionally, be further processed to provide aproduct having a higher purity, for example a monoester content of above90%.

Typical further processing would involve the removal of glycerol and thesubsequent distillation of the resulting mixture. By means of thisfurther processing an end product with a typical glycerol monoestercontent above 90% may be provided. The fatty acid profile of the endproduct would reflect the fatty acid profile of the castor oil startingmaterial. This process, namely the production of a glycerol monoester,is described in Bailey's Industrial Oil & Fat Products, vol. 4, Fifthed. P.572 ff.

The glycerol monoester may then be reacted with an excess of aceticanhydride resulting in acetic acid being esterified with the glycerolester. Any excess of acetic anhydride is removed from the reactionmixture. The end product is a fully acetylated monoglyceride based oncastor oil (which may be hardened or unhardened castor oil).

Route 2

Route 2 provides a further manner in which acetylated monoglyceridesbased on, for example, hardened and unhardened castor oil may besynthesised. An acetylated monoglyceride may be produced by the reactionof castor oil with acetic anhydride to provide an acetylated castor oil.The acetylated castor oil is then reacted with triacetin to produceacetylated monoglycerides based on hardened and unhardened castor oil.This process is illustrated below.

Castor oil is reacted with acetic anhydride to produce an acetylatedcastor oil. The degree of acetylation may be defined as castor oilcontaining at least one acetic acid group and up to the average of threeacetic acid groups per mole of castor oil. The acetylated castor oil isthen reacted with triacetin to produce a reaction mixture of mainlyacetylated glycerolesters with a fatty acid profile similar to that ofthe castor oil starting material. This mixture is purified bydistillation. The end product is an acetylated monoglyceride based onhardened or unhardened castor oil.

A process for obtaining acetylated glycerol esters from the reaction ofa triglyceride and triacetin is described in the Danish Patent No. 93786. The synthesis of acetylated monoglycerides based on castor oil fromthe starting materials acetylated castor oil and triacetin is analogousto that process.

In a highly preferred aspect the compound of the present invention isselected from compounds of the formula

These preferred compounds may be prepared and are preferably prepared inaccordance with Route 1 or Route 2 above.

The above compounds are specific compounds which may be provided by thepresent invention. In a broad aspect, the present invention furtherprovides a compound of the formula

wherein two of R₄, R₅, and R₆ are of the formula

wherein for each of the two of R₄, R₅, and R₆ q is independentlyselected from 0 to 4 or from 0 to 3; and the other of R₄, R₅, and R₆ isa branched group of the formula

wherein n is from 10 to 20 and m is 2n, and wherein p is from 0 to 4 orfrom 0 to 3.

Preferably q is 0. More preferably for both of the two of R₄, R₅, and R₆is 0.

Preferably n is from 16 to 20, more preferably from 16 to 18, yet morepreferably 17.

Preferably the group CnHm is a straight chain hydrocarbon group.

In a preferred aspect the branched group is a group of the formula

wherein x is from 7 to 10, preferably x is 10, and y is 2x, and whereinp is from 0 to 4 or from 0 to 3, preferably p is 0.

Preferably the group CxHy is a straight chain hydrocarbon group.

The compounds provided by the present invention may be incorporated in acomposition comprising a thermoplastic polymer. Accordingly in a furtheraspect the present invention provides a composition comprising acompound as defined above and a thermoplastic polymer.

The thermoplastic polymer of the compositions of the present inventionmay be or comprise a vinyl chloride polymer or a vinyl chloridecopolymer selected from vinyl chloride/vinyl acetate copolymer, vinylchloride/vinylidene chloride copolymer, vinyl chloride/ethylenecopolymer and a copolymer prepared by grafting vinyl chloride ontoethylene/vinyl acetate copolymer, or a mixture thereof.

In a preferred aspect the thermoplastic polymer is or comprises apolymer blend of a thermoplastic polymer, preferably a thermoplasticpolymer as defined above, and a second polymer. Preferably, the secondpolymer is a methacryl polymer or an acrylonitrile-butadiene-styrenepolymer.

The compositions of the present invention may be formulated in anymanner to provide the required plasticising properties of the compound.In a particular aspect the composition of the present inventioncomprises the compound in an amount of 1 to 100 parts by weight per 100parts by weight of the thermoplastic polymer.

PROCESS OF INVENTION

As disclosed above the present invention provides a process for thepreparation of a compound having the formula

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 5 or from 2 to 6 carbon atoms,wherein at least one of R₁, R₂ and R₃ is a branched chain acyl group (along acyl group) consisting of or having a chain having 10 to 20 carbonatoms and a hydrophilic branch group, the process comprising the stepsof: (i) interesterification between glycerol and triglyceride compoundhaving the formula

wherein each of R₁, R₂ and R₃ is a fatty acid group consisting of orhaving a chain having 10 to 20 carbon atoms, to provide a compositioncomprising glycerol, monoglyceride, diglyceride and/or triglyceride;(ii) optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same.

In the process of the present invention the chain having 10 to 20 carbonatoms may be saturated or unsaturated.

In preferred aspects the compound prepared by the process is a compoundof the present invention as described herein. In a broader aspects

-   -   the long acyl group is of the formula        -   wherein n is from 10 to 20 and m is selected from 2n, 2n−2,            2n−4 and 2n−6, and wherein p is from 0 to 4 or from 0 to 3.        -   Preferably m is 2n or 2n−2.        -   Preferably the group CnHm is a straight chain hydrocarbon            group. The straight chain hydrocarbon group may be saturated            or unsaturated. The straight chain hydrocarbon group may            contain a single —C═C— bond.    -   the long acyl group is a group of the formula        -   wherein x is from 7 to 10, preferably x is 10, and y is            2x−2, and wherein p is from 0 to 4 or from 0 to 3,            preferably p is 0.        -   Preferably the group CxHy is a straight chain hydrocarbon            group. The straight chain hydrocarbon group may be saturated            or unsaturated. The straight chain hydrocarbon group may            contain a single —C═C— bond.    -   the long acyl group is a group of the formula    -   the compound is of the formula    -   the compound is of the formula        -   wherein two of R₄, R₅, and R₆ are of the formula        -   wherein for each of the two of R₄, R₅, and R₆ q is            independently selected from 0 to 4 or from 0 to 3        -   and the other of R₄, R₅, and R₆ is a branched group of the            formula        -   wherein n is from 10 to 20 and m is selected from 2n, 2n−2,            2n−4 and 2n−6, and wherein p is from 0 to 4 or from 0 to 3.            Preferably q is 0. More preferably for both of the two of            R₄, R₅, and R₆ q is 0. Preferably n is from 16 to 20, more            preferably from 16 to 18, yet more preferably 17. Preferably            m is 2n−2.    -   the branched group is a group of the formula

wherein x is from 7 to 10, preferably x is 10, and y is 2x−2, andwherein p is from 0 to 4 or from 0 to 3, preferably p is 0.

The invention will now be described in further detail with in thefollowing Examples.

EXAMPLES

Plasticisers Evaluated

Six plasticisers were evaluated. These were:

-   1. dioctyl phthalate (DOP)—a conventional phthalate based    plasticiser. DOP is by far the most widely used plasticiser for PVC.    DOP is available from Monsanto Europe, Belgium-   2. Diisononyl phthalate (DINP)—a conventional phthalate based    plasticiser from Monsanto Europe, Belgium-   3. Compound A—a compound having the structure-   4. Compound B—a compound having the structure-   5. Compound C—a compound having the structure-   6. Compound D—a compound having the structure    DOP, DINP and compound A are comparative compounds not in accordance    with the compound/composition of the present invention. Compounds B,    C and D are compounds containing saturated long chains in accordance    with the present invention.    Synthesis

The compounds were prepared as follows.

Synthesis of Compound A (Process of the Invention)

100 gram of castor oil, 30 gram of glycerol and 0.3 gram of 50% sodiumhydroxide is heated to 250° C. and reacted for 60 minutes. The sodiumhydroxide is neutralised with 0.5 gram of 85% phosphoric acid. Theglycerol is removed by water vapour distillation at 140° C. and 0.05mbar. The monoglyceride is concentrated by short path distillation at200° C. and a pressure below 5*10⁻³ mbar. 40 gram of monoglyceride isthen reacted with 40 gram of acetic anhydride at 140° C. for 60 minutesand the formed acetic acid is removed by vacuum distillation. The yieldof compound A is 50 gram.

The synthesis provided a composition (Composition A) containingapproximately 90 wt. % of a plasticiser compound A.

Synthesis of Compound B (Compound of the Invention)

100 gram of hydrogenated castor oil is reacted with 32 gram of aceticanhydride at 140° C. for 60 minutes and the formed acetic acid isremoved by vacuum distillation. 100 gram of the fully acetylatedhydrogenated castor oil is reacted with 100 gram of triacetin, 0.0045 ofsodium methoxide and 0.825 gram of aluminium stearate at 250° C. for 60minutes. The non reacted triacetin is removed by vacuum distillation at135° C. and 0.01 mbar. Compound B is concentrated by short pathdistillation at 200° C. and a pressure below 5*10⁻³ mbar. The yield ofcompound B is 40 gram.

The synthesis provided a composition (Composition B) containingapproximately 90 wt. % of a plasticiser compound B.

Synthesis of Compound C (Compound and Process of the Invention)

100 gram of hydrogenated castor oil, 30 gram of glycerol and 0.3 gram of50% sodium hydroxide is heated to 250° C. and reacted for 60 minutes.The sodium hydroxide is neutralised with 0.5 gram of 85% phosphoricacid. The glycerol is removed by water vapour distillation at 140° C.and 0.05 mbar. The monoglyceride is concentrated by short pathdistillation at 200° C. and a pressure below 5*10⁻³ mbar. 40 gram ofmonoglyceride is then reacted with 54 gram of butyric anhydride at 150°C. for 90 minutes and the formed butyric acid is removed by vacuumdistillation. The yield of compound C is 61 gram.

The synthesis provided a composition (Composition C) containingplasticiser compound C.

Synthesis of Compound D (Compound and Process of the Invention)

100 gram of hydrogenated castor oil, 30 gram of glycerol and 0.3 gram of50% sodium hydroxide is heated to 250° C. and reacted for 60 minutes.The sodium hydroxide is neutralised with 0.5 gram of 85% phosphoricacid. The glycerol is removed by water vapour distillation at 140° C.and 0.05 mbar. The monoglyceride is concentrated by short pathdistillation at 200° C. and a pressure below 5*10⁻³ mbar. 40 gram ofmonoglyceride is then reacted with 74 gram of hexanoic acid anhydride at160° C. for 90 minutes and the formed hexanoic acid is removed by vacuumdistillation. The yield of compound D is 67 gram.

The synthesis provided a composition (Composition D) containingplasticiser compound D.

Example 1

Plasticiser composition B is tested for its function as a plasticiserusing the following formulation.

Formulation PVC (K = 70), Vestolit S7054* 100 parts by weight Ca—Znstabilizer  1 parts by weight Epoxidised soybean oil  3 parts by weightPlasticiser composition  50 parts by weight *available from Hüls AG,GermanyTest Procedure

A predetermined amount of plasticiser composition is added to the aboveformulation and the mixture kneaded at 150 to 155° C. for 5 minutesbetween 20 cm test rollers. The rolled sheet is further pressed at 160°C. and 150 kg/cm² using a compression molding machine to form a 1-mmthick sheet.

The test procedure demonstrates that Composition B provides aplasticising effect.

Example 2

Plasticiser composition B and the four plasticisers of Example 2 of U.S.Pat. No. 4,426,477 are tested for their function as a plasticiser usinga PVC paste resin formulation.

Formulation PVC (K = 78), Vestolit P1348K* 100 parts by weight Ca—Znliquid stabilizer  3 parts by weight Plasticiser composition  60 partsby weight *available from Hüls AG, GermanyTest Procedures

Bleeding Property—after dearation the compositions are spread over aglass plate to form a 1 mm thick film. The film is allowed to gel for 15minutes in an oven at 180° C. The resulting sheet is left to stand atroom temperature for a week. The bled matter is washed off with anacetone/IPA mixture. The sheet is dried to measure its weight loss.

The test procedure demonstrates that Composition B bleeds less than eachof the compositions of U.S. Pat. No. 4,426,477.

Example 3

Plasticiser composition B is evaluated by using an ethylene/vinylchloride copolymer sheet formulation.

Formulation Ethylene/vinyl copolymer (K = 55)* 100 parts by weight Ca—Znstabiliser  2.0 parts by weight Methylmethacryl-butadiene-styrene resin 5.0 parts by weight Lubricant, stearic acid monoglyceride  1.0 parts byweight Polyethylene wax  0.3 parts by weight Plasticiser composition 3.0 parts by weight *available from Hüls AG, GermanyTest Procedure

The above formulation is kneaded at 180 to 190° C. for 5 minutes between20 cm test rollers. The processability is judged at this point. Next,the rolled sheet is further pressed at 180° C. and 100 kg/cm² to form a1 mm thick sheet, and then the transparency is measured.

The test procedure demonstrates that Composition B provides a polymercomposition having good processability and good transparency.

Example 4

Plasticiser composition B is evaluated by using a PVC wrap formulation.

Formulation PVC (K = 70), Vestolit S7054 100 parts by weight Epoxidisedsoybean oil  10 parts by weight Ca—Zn stabiliser  2 parts by weightChelator  0.5 parts by weight Antifogging agent sorbitan laurate  1.0parts by weight Polyoxyethylene alkyl ether  1.0 parts by weightPlasticiser composition  35 parts by weightTest Procedure

The above formulation is moulded into a wrap film by use of a 19 mmextruder and the film is subjected to tests for evaluation ofproperties.

Specifications of Extruder

A Brabender extrusiograph Type 19/25 D

Screw diameter 19 mm, L/D=25, die 25 mm wide die

Screw compression ration 2:1

Extrusion Conditions Cylinder head temperature 195° C. Die temperature205° C. Screw speed  35 rpm Take-off speed  12 m/min

The test procedure demonstrates that Composition B provides a polymercomposition having good processability, good transparency, bleeding andantifogging properties.

Example 5

Each of the six compounds being evaluated were incorporated in PVC.

The compounds were incorporated in the PVC in the following amounts.

PVC (K = 70), Solvic S 271 GC* 100 parts by weight Plasticiser  40 partsby weight *available from Solvay & Cie, Belgium

The PVC and plasticiser compounds were mixed in a Brabender PlanetaryMixer Type P 600. The mixer was operated at 88° C. and 100 RPM. Theprocedure is in accordance with ISO/DIS 4574.

The individual compounds are compression moulded into sheets having athickness of approximately 4 mm in accordance with ISO 293-1974.Conditions were 190° C. and an applied pressure of 7.5 bar. Mouldingtime was set to 150 seconds.

Dumbbell test specimens were cut from the compression moulded sheetsaccording to DIN 53457 (Dumbbell no. 4). The properties measured toevaluate the plasticiser effect are shown in the table below. Shore Awas measured according to DIN 53505. All other properties were recordedin accordance with DIN 53457.

Results

Youngs Modulus Strain at Break Stress at Break Shore A Shore A SASE(100%) Plasticiser [Mpa] [%] [Mpa] (after 3 sec.) (after 15 sec.) [Mpa]DOP 12.04 639.3 22.20 92.5 90.0 8.46 DINP 15.04 687.4 24.08 94.0 91.59.31 Compound A 16.14 678.7 28.01 91.0 88.0 10.40 Compound B 12.96 733.024.98 91.0 88.0 9.07 Compound C 25.89 690.4 23.83 95.0 92.0 10.51Compound D 101.20 474.8 19.89 98.0 97.0 12.88

The parameters typically used to describe the plasticising effect isYoung's Modulus and Shore A values.

-   -   Young's Modulus is also called the elasticity modulus and the        lower the value of this parameter the better is the plasticising        effect.    -   Shore A is a measure of the hardness of the product. This value        should in general be as low as possible.

The stress required for a 100% elongation of the test specimen (SASE,100%) is also used to evaluate the properties of a plasticiser. A lowvalue on this parameter indicates a good plasticising effect.

The “Strain at Break” and “Stress at Break” are two additionalmechanical properties that are used to describe a plasticised PVC.

In comparison to the industry standard plasticiser DOP, Compound Bprovided analogous performance to DOP. Compound B provided superiorperformance when compared to Compound A and DINP. Compound C and Dexhibited a plasticising effect but exhibited inferior performancecompared to Compound B.

Example 6

Each of the six compounds being evaluated were incorporated in PVC.

The compounds were prepared in accordance with Example 5 andincorporated in the PVC in the following amounts.

PVC (K = 70), Solvic S 271 GC* 100 parts by weight Plasticiser  60 partsby weight *available from Solvay & Cie, Belgium

Youngs Modulus Strain at Break Stress at Break Shore A Shore A SASE(100%) Plasticiser [Mpa] [%] [MPa] (after 3 sec.) (after 15 sec.) [Mpa]DOP 3.87 878.4 17.71 79.0 76.5 3.81 DINP 4.46 882.0 19.15 83.5 80.0 4.31Compound A 4.99 815.0 18.49 79.0 75.5 4.70 Compound B 4.19 868.2 18.4280.5 78.0 3.88 Compound C 6.65 756.0 18.05 88.0 85.0 5.48 Compound D64.43 487.5 18.23 97.0 93.5 10.73

Results for this formulation which contains 60 parts plasticiser shows abetter plasticising effect for all products in comparison to the resultsobtained with the formulation of Example 5 (40 parts plasticiser).

As for Example 5 in comparison to industry standard DOP, Compound Bprovided analogous performance to DOP, in particular in respect ofYoung's Modulus, SASE (100%) and Shore A. Compound B provided superiorperformance when compared to Compound A and DINP. Compound C and Dexhibited a plasticising effect but exhibit inferior performance thanCompound B.

All publications mentioned in the above specification are hereinincorporated by reference. Various modifications and variations of thedescribed methods and system of the invention will be apparent to thoseskilled in the art without departing from the scope and spirit of theinvention. Although the invention has been described in connection withspecific preferred embodiments, it should be understood that theinvention as claimed should not be unduly limited to such specificembodiments. Indeed, various modifications of the described modes forcarrying out the invention which are obvious to those skilled inchemistry or related fields are intended to be within the scope of thefollowing claims.

1. A compound of the formula

wherein two of R₄, R₅, and R₆ are of the formula

wherein for each of the two of R₄, R₅, and R₆ q is independentlyselected from 0 to 3 and the other of R₄, R₅, and R₆ is a branched groupof the formula

wherein n is from 10 to 20 and m is 2n, and wherein p is from 0 to 4,and wherein one of p and is greater than
 0. 2. A compound according toclaim 1 wherein p is from 1 to
 3. 3. A compound according to claim 1wherein q is
 0. 4. A compound according to claim 1 wherein n is from 16to
 20. 5. A compound according to claim 1 wherein the branched group isa group of the formula

wherein x is from 7 to 10 and y is 2x, and wherein p is from 0 to
 4. 6.A compound according to claim 5 wherein p is from 0 to
 3. 7. A compoundaccording to claim 5 wherein p is
 0. 8. A compound according to claim 5,wherein x is
 10. 9. A compound of the formula


10. A compound of the formula


11. A process for the preparation of a compound having the formula

wherein R₁, R₂, and R₃ are independently selected from an acyl group ora hydrogen atom, wherein at least one of R₁, R₂, and R₃ is an acyl group(a short acyl group) having from 2 to 6 carbon atoms; wherein at leastone of R₁, R₂, and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula

wherein each of R₁, R₂, and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglycende and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same.
 12. A compound of claim 1, wherein n isfrom 16 to
 18. 13. A compound of claim 1, wherein n is
 17. 14. A processfor the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 1.15. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglycende or thecomposition containing the same, wherein the compound is as in claim 2.16. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 3.17. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride andlor diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 4.18. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 5.19. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 6.20. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having of a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 7.21. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 8.22. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 9.23. A process for the preparation of a compound having the formula:

wherein R₁, R₂ and R₃ are independently selected from an acyl group or ahydrogen atom, wherein at least one of R₁, R₂ and R₃ is an acyl group (ashort acyl group) having from 2 to 6 carbons atoms; wherein at least oneof R₁, R₂ and R₃ is a branched chain acyl group (a long acyl group)having a chain having 10 to 20 carbon atoms and a hydrophilic branchgroup; the process comprising the steps of: (i) interesterificationbetween glycerol and a triglyceride compound having the formula:

wherein each of R₁, R₂ and R₃ is a fatty acid group having a chainhaving 10 to 20 carbon atoms, to provide a composition comprisingglycerol, monoglyceride, diglyceride and/or triglyceride; (ii)optionally isolating the monoglyceride and/or diglyceride from thecomposition; (iii) acylating the monoglyceride and/or diglyceride or thecomposition containing the same, wherein the compound is as in claim 10.